Styryl dyestuffs

ABSTRACT

WATER-INSOLUBLE STYRYL DYESTUFFS OF THE FORMULA   1-(NC-C(-X)=CH-),2-Y1,4-(B-S-A-N(-R)-),5-Y2-CYCLOHEXANE   IN WHICH X REPRESENTS A CYANO, CARBO-LOWER ALKOXY OR PHENYLSULPHONE GROUP, Y1 AND Y2 EACH REPRESENTS A HYDROGEN, R REPRESENTS A LOWER ALKYL, PHENYL-LOWER ALKYL, GROUP, R REPRESENTS ALOWER ALKYL, PHENYL-LOWER ALKYL, CYANO-LOWER ALKYL, LOWER ALKOXYALKYL OR ACYLOXYALKYL GROUP OR A RADICAL OF THE FORMULA-A-S-B, AND A REPRESENTS A LOWER ALKYLENE GROUP THAT MAY BE SUBSTITUTED BY A LOWER ALKONOYLOXY OR A BENZOLOXY GROUP AND B REPRESENTS A PHENYL GROUP.

United States Patent C) 3,784,558 STYRYL DYESTUFFS Richard Peter and Walter Jenny, Basel, Switzerland, assignors to Ciba-Geigy AG, Basel, Switzerland No Drawing. Continuation-impart of abandoned applicalion Ser. No. 662,313, Aug. 22, 1967. This application Oct. 13, 1970, Ser. No. 80,496 Claims priority, application Switzerland, Aug. 29, 1966, 12,485/66 Int. Cl. C07c 121/70 US. Cl. 260-465 D 7 Claims ABSTRACT OF THE DISCLOSURE Water-insoluble styryl dyestuifs of the formula a NC I R CROSS-REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of application Ser. No. 662,313, filed Aug. 22, 1967, now abandoned.

The present invention is based on the observation that new and valuable water-insoluble styryl dyestuffs of the formula Y I a R or an aldimine thereof is condensed with a compound of the formula NC R or (b) a styryl compound of the formula alkoxyalkyl or acyloxyalkyl group or a residue 3,784,558 Patented Jan. 8, 1974 -AZ, Z representing a halogen atom, and A, X, Y; and Y have the meanings given above, is condensed with an aryl, aralkyl or heterocyclic mercaptan.

The compounds of the Formula 2 which are used as starting materials may be obtained by condensing an arylmercaptoalkylaniline or an aralkylmercaptoalkylaniline of the formula l A- S -B in which A, B and R have the meanings given above, and especially those of the formula CHzCHgX OHC in which B represents a phenyl or benzthiazolyl residue which may be substituted by halogen atoms or alkyl or alkoxy groups and X represents a hydrogen atom or the residue -S-B.

Examples are as follows:

2-methyl-4-N-methyl-N-phenylmercaptoethylaminobenzaldehyde, 2-methyl-4-N-ethyl-N-phenylmercaptoethylaminobenzaldehyde, Z-methyl-4-Nethyl-N-para-chlorophenylmercaptoethylaminobenzaldehyde, 2-methyl-4-N-ethyl-N-(2',5-dichlorophenyl)-mercaptoethylaminobenzaldehyde, 2-methyl-4-N-ethyl-N-(2,4'-dichlorophenyl)-mercaptoethylaminobenzaldehyde, 2-methyl-4-N-ethyl-N-para-methylphenylmercaptoethylaminobenzaldehyde, 2-methyl-4-N-ethyl-N-(2',5'-dimethylphenyl)-mercaptoethylaminobenzaldehyde, Z-methyl-4-N-ethyl-N-ortho-methoxyphenyl-mercaptoethylaminobenzaldehyde, 2-methy1-4N-ethyl-N- (2',5 '-dimethoxyphenyl) -mercaptoethylaminobenzaldehyde, 2-methyl-4-N-ethyl-N-ortho-nitrophenylmercaptoethylaminobenzaldehyde, 2-methyl-4-N-ethyl-N-para-nitrophenylmercaptoethylaminobenzaldehyde, 2-methyl-4-N-ethyl-N-ortho-carbomethoxyphenylmercaptoethylaminobenzaldehyde, 2-methyl-4-N-ethyl-N-para-carbethoxy-phenylmercaptoethylaminobenzaldehyde, 2-methyl-4-N-cyanoethyl-N-phenylmercaptoethylaminobenzaldehyde, 2-methy1-4-N'methoxyethyl-N-phenylmercaptoethylaminobenzaldehyde, Z-rnethyl-4-N-acetoxyethyl-N-phenylmercaptoethylaminobenzaldehyde,

Z-methyl-4-N-benzyl-N-phenylmercaptoethylaminobenzaldehyde, Z-methyl-4-N-5-phenylethyl-N-phenylmercaptoethylaminobenzaldehyde, 2-methyl-4-N-ethyl-N-phenylmercaptoethylarninobenzaldehyde, 2-methyl-4-N-n-propyl-N-phenylmercaptoethylaminobenzaldehyde, 2-methyl-4-N-n-butyl-N-phenylmercaptoethylaminobenzaldehyde, 2-methyl-4-N-ethyl-N- (2'-benzthiazolyl) -mercaptoethylaminobenzaldehyde, and 2-methyl-4-N,N-bis-(phenylmercaptoethyl) -aminobenzaldehyde.

Condensation of the aldehydes of the Formula 2 with the cyano compound of the formula is advantageously carried out with the application of heat in the presence of a basic catalyst, for example, ammonia, dimethylamine, .diethylamine, piperidine, piperidine, acetate, sodium or potassium alcoholate, if necesary, in the presence of a solvent for example, methanol, ethanol, benzene, toluene, xylene, chloroform or carbon tetrachloride. When using solvents, the water formed during the reaction can be removed continuously from the reaction mixture by azeotropic distillation of the solvent, whereby the reaction equilibrium is shifted constantly in favor of the condensation product. Condensation may also be effected without a basic catalyst in glacial acetic acid or in some other organic acid, or in the absence of a solvent by fusing the reactants together in the presence of a basic catalyst, for example, ammonium acetate or piperidine acetate.

The aldehydes can be replaced by the aldimines thereof, that is to say, the condensation products obtained with primary amines, especially aminobenzenes, in other words, the so-called Schiffs bases of the formula in which R, preferably represents a benzene residue, for example, a phenyl or sulphophenyl residue. The compounds of the Formula 7 may be obtained by condensing the product obtained by reacting formaldehyde and a compound of the formula in which X represents a hydrogen or a halogen atom and Z represents a halogen atom or an arylsulphonyloxy group.

These are condensed, for example, with the following mercaptans:

phenylmercaptan,

2-, 3- or 4-chlorophenylmercaptan, 2,4- or 2,5-dichlorophenylmercaptan, 2-, 3- or 4-methylphenylmercaptan, 2,4- or 2,5-dimethylphenylmercaptan, 2-, 3- or 4-methoxyphenylmercaptan, 2,4- or 2,5-dimethoxyphenylmercaptan, 2- or 4-nitrophenylmercaptan,

2- or 4-carbomethoxyphenylmercaptan, Z-mercaptobenzthiazole, 2mercapto-6-chlorobenzthiazole, Z-mercapto-4-chlorobenzthiazole, 2-mercapto-4-methylbenzthiazole, Z-mercapto-6-methylbenzthiazole, Z-mercapto-6-methoxybenzthiazole, Z-mercapto-6-ethoxybenzthiazole, Z-mercaptobenzoxazole, and Z-mercaptobenzimidazole.

The reaction with the arylmercaptan is advantageously carried out in an organic solvent, preferably an alcohol, in the presence of an alkali metal hydroxide, an alkali metal alcoholate or an alkali metal carbonate at an elevated temperature, advantageously at the boiling temperature of the alcohol. It is advantageous to use at least one mol of the alkali metal hydroxide or alkali metal carbonate for each mol of the halogen compound.

The new dyestuffs, which have a high melting point,

are suitable for dyeing and printing man-made fibres, for

example, cellulose acetate fibres, but especially aromatic polyester fibres, particularly after the dyestutfs have been converted into a state of fine division, for example, by grinding, pasting, reprecipitation and so forth. They produce pure, strong, greenish yellow dyeings possessing excellent fastness to light and sublimation on the said fibres by the conventional dyeing processes, for example,

when applied in a dyebath containing a fine dispersion of dyestuif and advantageously a dispersing agent at a temperature close to C., if necessary, in the presence of a swelling agent, or at a temperature above 100 C. under superatmospheric pressure. The new dyestuifs also have the advantage that they only very slightly stain wool and other fibres that may be present in the dyebath. They are therefore very suitable for dyeing union fabrics made from a mixture of polyester fibre and wool or, for example, a mixture of polyester fibre and cellulose triacetate. They may also be used for spin-coloration in bulk.

The dyestulfs of the invention are also suitable for application by the so-called Thermosol process in which the fabric to be dyed is impregnated at a temperature preferably not exceeding 60 C. with an aqueous dispersion of the dyestuff which advantageously contains 1 to 50% of urea and a thickening agent, especially sodium alginate and is then squeezed in the usual manner; advantageously so as to retain 50 to 100% of dye-liquor, based on the dry Weight of the goods. To fix the dyestutf, the material so impregnated is heated to a temperature above 100 C., for example, to a temperature between and 210 C., advantageously after drying, for example, in a current of warm air.

The Thermosol process described above is specially suitable for the dyeing of union fabrics made from polyester and cellulosic fibres, especially cotton. When used for this purpose, the padding liquor may contain dyestuffs suitable for dyeing cotton, for example, vat dyestuffs, in addition to the dyestuffs of the invention. When vat dyestuffs are used, the padded fabric must be treated with an aqueous alkaline solution of one of the reducing agents customarily used in vat dyeing subsequent to the heat treatment. The dyeings and prints obtained possess good properties of general fastness and, in particular, display good fastness to light and sublimation.

EXAMPLE 1 39.5 parts of N-ethyl-N-(p-chloroethyl) m toluidine and 39.4 parts of 2,5- dichlorothiophenol are boiled for 4 hours under reflux in a solution containing 4.6 parts of sodium in 100 parts by volume of absolute alcohol. The sodium chloride which forms is removed by filtration and the filtrate is evaporated. The N-ethyl-N-(2',5-dichlorophenylmercapto)-ethyl-m-toluidine which remains is distilled. It boils at 153 to 159 C. under a pressure of 0.02 mm. Hg.

13.6 parts of the compound so obtained are introduced at 15 C. into a mixture of 11.1 parts by volume of dimethylformamide and 9.4 parts by volume of phosphorus oxychloride and the batch is stirred for 5 hours at 60 C. It is discharged on to ice, chloroform is added, the mixture of ice and chloroform is neutralized with sodium hydroxide solution, the chloroform phase is washed with water, dried with sodium sulphate and evaporated. The aldehyde of the formula N C CzHn I CzHs-S-Q is isolated by suction filtration, washed with ethanol (about 95%) and dried in a vacuum cabinet. It melts at 139 to-l40 C.

In the following table is listed a series of further dyestuffs of the formula which may be obtained by the process described in this example and which also dye polyester fibres pure, greenish yellow shades possessing excellent fastness to light and 4.3 parts of 2,5-dichlorothiophenol are boiled for 3 hours under reflux in a solution containing 0.46 part of sodium in 100 parts by volume of absolute alcohol. The hot solution is separated from the sodium chloride which forms by filtration. The dyestutf crystallizes from the filtrate in the form of an orange powder melting at 136 to 138 C. It is identical with the dyestulf obtained by the process described in Example 1.

EXAMPLE 3 46.4 parts of N,N-bis- (fl-chloroethyl)-meta-toluidine and 63.6 parts of 4-chlorothiophenol are boiled for 4 hours under reflux in a solution containing 9.2 parts of sodium in 100 parts by volume of absolute alcohol. The sodium chloride which forms is removed by filtration, the filtrate is evaporated, the residue is dissolved in chloroform, washed and dried with calcium chloride. A pale yellow oil remains which eventually solidifies to white crystals. When recrystallized once from petroleum ether, the N,N bis-(fl-para-chlorophenylrnercaptoethyl)-metatoluidine melts at 72 to 76 C. 13.5 parts of this compound are introduced at 15 to 20 C. into a mixture of 5.6 parts by volume of dimethylformamide and 4.7 parts by volume of phosphorus oxychloride, and the batch is stirred for 5 hours at C. It is then discharged on to ice, chloroform is added and the mixture is neutralized with sodium hydroxide solution. The chloroform phase is washed with water, dried with sodium sulphate and evaporated. 14.4 parts of a yellowish oil remain which solidifies to a white cake of crystals.

The crude aldehyde of the formula 0 (HEP-SO01 H 4: \C zHr-S-O-Cl melts at 80 to C.

4.8 parts of the aldehyde so obtained are boiled for 4 hours under reflux together with 0.7 part of malodinitrile and 0.1 part by volume of piperidine in 20 parts by volume of absolute ethanol. After cooling to room temperature, the orange dyestuif of the formula is isolated by suction filtration, washed with a small amount of ethanol and then dried in a vacuum and subhmatmcabinet. It melts at to 132 0.

B R Y1 Y2 X 1 4-chlorophenyl Ethyl MethyL..- H Cyano.

2... 2,5-dichlorophenyl (in (in H Carbethoxy.

3 do do do H Phenyl-sulphonyl.

4 2-benzthiazo1yl do do H Cyano,

5 2,5-dichloropheuy1 Cyanoethy1.- H H Do.

6 do Benzyl H Do.

7 3,4-dichlorophenyl Ethyl Methy1 H Do.

8 2,5-dichlorophenyl do Methoxy H Do.

9 do do Methy1 Methyl.... Do.

10 3,5-di0h10r0phenyl do do do Do.

11.. 2,4-dichloro-5-methy1phenyl .d do do Do.

12.. 2,5-dichlorophenyl n-But Methoxy Do.

13 th H Do.

EXAMPLE 2 5.5 parts of the dyestufi' of the formula which may be obtained by the process described in this example and which dye polyester fibres pure, greenish yellow shades possessing excellent fastness to light and sublimation.

A dyestutf identical with dyestuif No. 1 of the table in Example 3 may be obtained when 1 mol of the dyestutf of the formula is treated with 2 mols of 3,5-dichlorothiophenol in the manner described in Example 2. It melts at 147 to 148 C.

Analysis.-Calculated (percent): CI, 23.90; S, 10.81. Found (percent): Cl, 23.80; S, 10.60.

EXAMPLE 200 parts of epichlorohydrin are added at to C. to a mixture of 270 parts of N-ethyl-meta-toluidine in 200 parts of water and 300 parts by volume of glacial acetic acid and the batch is stirred for 3 hours at 10 to 20 C. The readily volatile components are then distilled at a maximum temperature of 75 C. and finally in a high vacuum. 505 parts of an oil of the formula remain. 4.6 parts of sodium are dissolved in 200 parts by volume of absolute alcohol, 39.4 parts of 2,5-dichlorothiophenol are added and then a solution of 45.6 parts of the amine described above in 100 parts by volume of absolute alcohol is added while stirring and boiling under reflux. After stirring and boiling under reflux for 4 hours, the batch is cooled to room temperature, freed from sodium chloride by filtration, dissolved in benzene, washed successively with sodium carbonate solution and water, dried with sodium sulphate and concentrated. The residue is distilled in a high vacuum. 50 parts of the amine of the formula CzHi Cl CHr-C H-CHz- S 8 and concentrated. 28.3 parts of a brown oil remain which distills a high vacuum at 183 to 186 C. 0.015 mm. Hg. It corresponds to the formula 17.2 parts of this amine are dissolved in 12.5 parts by volume of dimethylformamide and 4.4 parts by volume of phosphorus oxychloride are added dropwise at 15 to 20 C. The batch is then stirred for 1 hour at C., discharged on to ice and stirred for some time. The hard mass which forms is treated with a 10% sodium carbonate solution and suction filtered. 14 parts of the aldehyde of theformula remain. This is condensed with 2.2 parts of malodinitrile in methanol in the usual manner and the dyestulf of the formula Cg /C2H6 Cl o=crr- N o N CH3"C H-CHas CCH:

is obtained.

It dyes cellulose acetate and polyester materials greenish yellow shades possessing good properties of fastness.

EXAMPLE 6 When esterification is carried out with benzoyl chloride instead of acetic anhydride and the procedure described in Example 5 is followed, the dyestufi of the formula is obtained which dyes hydrophobic materials, especially polyester fibres and fabrics, greenish yellow shades possessing excellent properties of fastness.

EXAMPLE 7 1 part of the dyestuff of the formula is ground wet with 2 parts of a 50% aqueous solution of I sulphite cellulose waste liquor and the batch is dried.

The dyestuff preparation so obtained is mixed with 40 parts of a 10% aqueous solution of a condensation product obtained from octadecyl alcohol and 20 mole of ethylene oxide and then 4 parts of a 40% acetic acid solution are added. A dyebath of 4,000 parts is prepared therefrom by dilution with water.

parts of cleaned polyester fibre material are entered into this dyebath at 50 C., the temperature is raised to to (1. within 30 minutes and dyeing is carried out for one hour at that temperature in a closed vessel.

The material is then well rinsed. A greenish yellow dyeing possessing excellent fastness to light and sublimation is obtained.

200 parts of the dyestuff preparation obtained in the manner described in Example 1 are stirred into 800 parts of the stock thickening so prepared by means of a highspeed stirrer until dispersion is complete. A polyethylene terephthalate fabric is printed with this paste. After printing, the fabric is dried, steamed for 45 minutes at atmosphere (gauge), rinsed for minutes in cold water, centrifuged and dried. A fast, greenish yellow print is obtained.

What is claimed is:

1. A water-insoluble styryl dyestulf of the formula 2 NC I R in which X represents cyano, carbalkoxy containing up to 3 carbon atoms or phenyl sulphone, Y and Y each represents hydrogen, methyl, methoxy or chlorine, R represents a C C -alkyl, phenyl-alkyl containing up to 8 carbon atoms, cyano-alkyl containing up to 3 carbon atoms, methoxyalkyl, fatty acid acyloxyalkyl containing up to 4 carbon atoms, or a radical of the formula and A represents an alkylene group containing up to 3 carbon atoms that may be substituted by fatty acid acyloxy containing up to 2 carbon atoms or benzoyloxy and B represents phenyl substituted by bromine, chlorine, nitro, methyl or methoxy.

2. A water-insoluble styryl dyestutf as claimed in claim 1 of the formula in which B' represents phenyl substituted by chlorine,

10 bromine, methyl, methoxy or nitro, X is a direct bond or a group of the formula in which R is methyl or phenyl and R is a C -C -alkyl group or the radical of the formula CH CH S-B'. 3. Water-insoluble styryl dyestutfs as claimed in claim 1 wherein X is CN.

4. The dyestufr of the formula 5. The dyestuif of the formula ozHrs 6. A dyestuif of the formula out-i1 HCHSQ com I] l 0 7. A dyestuif of the formula References Cited UNITED STATES PATENTS 2,583,614 1/1952 Taylor et al. 260-465 2,936,319 5/1960 Merian et al. 260-465 FOREIGN PATENTS 1,245,005 7/ 1967 Germany.

LEWIS GOTTS, Primary Examiner D. H. TORRENCE, Assistant Examiner US. Cl. X.R. 

